CN106083675A - A kind of methionine novel crystal forms I and preparation method thereof - Google Patents
A kind of methionine novel crystal forms I and preparation method thereof Download PDFInfo
- Publication number
- CN106083675A CN106083675A CN201610391281.7A CN201610391281A CN106083675A CN 106083675 A CN106083675 A CN 106083675A CN 201610391281 A CN201610391281 A CN 201610391281A CN 106083675 A CN106083675 A CN 106083675A
- Authority
- CN
- China
- Prior art keywords
- methionine
- crystal formation
- solution
- diffraction
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C319/00—Preparation of thiols, sulfides, hydropolysulfides or polysulfides
- C07C319/26—Separation; Purification; Stabilisation; Use of additives
- C07C319/28—Separation; Purification
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/57—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups
- C07C323/58—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton the carbon skeleton being further substituted by nitrogen atoms, not being part of nitro or nitroso groups with amino groups bound to the carbon skeleton
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of methionine crystal formation I, described crystal formation I angle of diffraction 2 θ 21.751 ± 0.2 °, 22.168 ± 0.2 °, 21.186 ± 0.2 °, 25.426 ± 0.2 °, 18.395 ± 0.2 °, have diffraction maximum at 32.879 ± 0.2 °.Methionine crystal formation I of the present invention is that white crystals granule, reflective are good; its granule is big, in near-spherical and granularity concentrates on 110 130 microns, more uniform, excellent quality; its dissolubility is good simultaneously; in water, dissolubility is more than 4.5g/100g water, uses it for efficiency height during liquid preparation produces, is beneficial to large-scale industrial use production.
Description
Technical field
The present invention relates to a kind of methionine novel crystal forms and preparation method thereof.
Background technology
Methionine (DL-Methionine) chemical formula is C5H11O2NS, white flakes crystallization or crystalline powder, there is spy
Different abnormal smells from the patient, taste is micro-sweet.For nutritional supplement, add in Herba bromi japonici, rye (Secale cereale L.), rice, Semen Maydis, Semen Tritici aestivi, peanut powder, Semen sojae atricolor, Rhizoma Solani tuber osi, Herba Spinaciae
Deng in food to improve amino acid balance, requirement is different with cystine intake, adult man's requirement be 1.1g/d.Also use
In amino acid transfusion, comprehensive amino acid preparation, can be used as spice by China GB2760-86 regulation, it or one are essential
Animal feed additive, the animal feed added with methionine can help animal Fast Growth at short notice so that it is save
The feedstuff of about 40%.Poultry lack methionine, can cause dysplasia, lose weight, Liver and kidney miopragia, amyotrophy,
Fur is rotten.
Chinese patent CN104926701 A discloses the purifying process of a kind of methionine, uses macroporous adsorbent resin to separate
Methionine and by-product salts substances, methionine is attracted on macroporous adsorbent resin then reclaim egg ammonia with strippant desorbing resin
Acid, by-product salts substances is not entered in absorption effluent by absorption with macroporous adsorbent resin in adsorption process, mainly includes following
Step: 1) resin absorption: methionine solution passes through macroporous adsorbent resin layer, when containing methionine in resin column effluent
When content is more than or equal to 10% (w/w) of import content, stop resin absorption；Resin absorption effluent is as by-product salt thing
Matter；2) resin desorption: step 1) in complete the resin of absorption, pass through with strippant, desorbing resin, and collect solution
Imbibition；3) subsequent technique process: stripping liquid is according to existing technological process subsequent treatment.Through Adsorption and desorption technique, available pure
The methionine product of degree >=99%, methionine content≤0.03% in by-product salts substances, resin extraction methionine yield >=
98%.Chinese patent CN104177280 A discloses a kind of methionine production technology, step 1: passed through by methionine crystalline mother solution
The continuous chromatography piece-rate system being filled with sodium form or potassium type chromatography resin separates, and obtains methionine solution and inorganic salt solution；Step
Rapid 2: methionine solution uses counter-infiltration system be concentrated to give methionine reverse osmosis concentrated liquid, by reverse osmosis concentrated for the methionine obtained
Contracting liquid returns Crystallization Procedure；This technique is simple, good separating effect, the advantages such as methionine purity is high, concentrated cost is low.
China granted patent CN101480385 B discloses the purposes of a kind of methionine, and methionine is in preparation treatment or pre-
Purposes in the compositions of anti-vestibulum auris internae hair cell disease, contains in its pharmaceutical composition: (a) 50-200 weight portion methionine
And/or its polypeptide；The pharmaceutically acceptable carrier of (b) 400-2000 weight portion；And the weight of (a)+(b) is that pharmaceutical composition is total
The 50-99% of weight, described pharmaceutical composition is solid preparation or liquid preparation, described liquid preparation include opacifiers,
Solution, suspending agent, syrup, drop etc..
The granules of methionine product solubility produced at present is relatively low, at about 3g/100g, use it in liquid preparation raw
Produce inefficient, there is certain limitation.
Summary of the invention
It is an object of the invention to provide the methionine novel crystal forms I that a kind of dissolubility is good.
Another object of the present invention is to provide the preparation method of above-mentioned methionine novel crystal forms I.
The object of the invention is achieved through the following technical solutions:
A kind of methionine crystal formation I, it is characterised in that: described crystal formation angle of diffraction 2 θ 21.751 ± 0.2 °, 22.168
± 0.2 °, 21.186 ± 0.2 °, 25.426 ± 0.2 °, 18.395 ± 0.2 °, have diffraction maximum at 32.879 ± 0.2 °.This crystal formation produces
Product dissolubility is excellent.
Specifically, methionine crystal formation I of the present invention angle of diffraction 2 θ 18.395 ± 0.2 °, 21.186 ± 0.2 °,
21.751±0.2°、22.168±0.2°、23.301±0.2°、25.426±0.2°、32.879±0.2°、33.775±
0.2 °, 37.054 ± 0.2 °, have diffraction maximum at 42.455 ± 0.2 °.
Above-mentioned methionine crystal formation I, it is characterised in that: it has followingValue and relative intensity percentage ratio I (%) value
Express-X-ray powder diffraction data,
Specifically, above-mentioned methionine crystal formation I, it is characterised in that: it has followingValue and relative intensity percentage
Express than I (%) value-X-ray powder diffraction data,
More specifically, above-mentioned methionine crystal formation I, it is characterised in that: it has X-ray powder diffraction as shown in Figure 1
Figure.
The melting point peak temperature of above-mentioned methionine crystal formation I is 282 DEG C, and this crystal formation has DSC/TG collection of illustrative plates as shown in Figure 2.
Methionine crystal formation I of the present invention is identical with methionine chemical constitution, and quality better, to be used for producing liquid preparation raw
Product efficiency is high.
The preparation method of methionine crystal formation I of the present invention, employing following steps:
1,5-(β-first mercaptoethyl) hydantoin react with solution of potassium carbonate obtain containing methionine potassium hydrolyzed solution
The hydroxypropyl methyl cellulose of middle addition 50-1000ppm, is passed through CO while stirring2、CO2The pressure that is passed through be 0.2-0.6Mpa,
Carry out crystallization and obtain methionine crude product；
2, above-mentioned methionine crude product is dissolved in sec-butyl alcohol solvent with the concentration of 10mg/mL-50mg/mL, is stirred continuously,
It is heated to 60 DEG C～100 DEG C dissolvings, filters, form supersaturated solution；The sealing of this solution is placed in-5 DEG C～-10 DEG C of environment
Crystallisation by cooling 1-3 hour, obtains white crystal.
The present invention has a following beneficial effect:
Methionine crystal formation I of the present invention is that white crystals granule, reflective are good, and its granule is big, in near-spherical and granularity is concentrated
In 110-130 micron, more uniform, excellent quality, its dissolubility is good simultaneously, and in water, dissolubility is more than 4.5g/100g water, will
Efficiency in liquid preparation produces is high for it, be beneficial to large-scale industrial use produces.
Accompanying drawing explanation
Fig. 1 is crystal type methionine X-ray powder diffraction figure of the present invention；
Fig. 2 is differential scanning calorimeter (DSC)/thermogravimetric analysis (TG) figure of crystal type methionine of the present invention；
Fig. 3 is the crystal type methionine of the present invention scanning electron microscope (SEM) photograph under 300 times.
Detailed description of the invention
Below by embodiment, the present invention is specifically described, it is necessary to it is pointed out here that be that following example are only used
In being further described the present invention, it is impossible to be interpreted as limiting the scope of the invention, person skilled in art can
The present invention made some nonessential improvement and adjustment according to the invention described above content.
Embodiment 1
The preparation method of methionine crystal formation I, as follows:
5-(β-first mercaptoethyl) hydantoin react with solution of potassium carbonate obtain containing in methionine potassium hydrolyzed solution
Add the hydroxypropyl methyl cellulose of 200-300ppm, be passed through CO while stirring2、CO2The pressure that is passed through be 0.3Mpa, tie
Partial crystallization goes out to obtain methionine crude product；
Above-mentioned methionine crude product is dissolved in sec-butyl alcohol solvent with the concentration of 25mg/mL-28mg/mL, is stirred continuously, adds
Heat, to 70 DEG C～75 DEG C dissolvings, filters, and forms supersaturated solution；This solution is sealed and is placed on crystallisation by cooling in-6 DEG C of environment
2.5 hours, obtain white crystal.
Embodiment 2
By the methionine crystal obtained by embodiment 1, it is XRD and tests:
Radiation source is Cu target, and wavelength is 1.54060nm, and scanning angle is 10 °～70 °, and voltage is 30kV, and electric current is
20mA, scanning speed is 2.4 °/min.Its X-ray powder diffraction figure is as shown in Figure 1.
Described crystal type methionine angle of diffraction 2 θ 118.395 ± 0.2 °, 21.186 ± 0.2 °, 21.751 ±
0.2°、22.168±0.2°、23.301±0.2°、25.426±0.2°、32.879±0.2°、33.775±0.2°、37.054
± 0.2 °, have diffraction maximum at 42.455 ± 0.2 °.
The crystal type methionine of the present invention, its powder X-ray diffraction pattern is with interplanar distance D, Bragg angle (2 θ), relative intensity
Percentage ratio I (%) and intensity (I value) crystal formation are expressed, as follows:
The differential scanning calorimeter (DSC) of crystal type methionine of the present invention is as in figure 2 it is shown, its endothermic transition temperature is 282
℃；Its thermogravimetric analysis figure (TG) is as in figure 2 it is shown, about 240 DEG C proceed by first reaction, and 282 DEG C carry out second reaction,
Terminate to reaction when 380 DEG C.
Methionine crystal type granule scanning electron microscope (SEM) photograph under 300 times as it is shown on figure 3, its granule is relatively big, in near-spherical and
Granularity concentrates on 110-130 micron, more uniform, excellent quality；After measured, its in water dissolubility at 5.0g/100g water.
Embodiment 3
The preparation method of methionine crystal formation I, employing following steps:
5-(β-first mercaptoethyl) hydantoin react with solution of potassium carbonate obtain containing in methionine potassium hydrolyzed solution
Add the hydroxypropyl methyl cellulose of 50-100ppm, be passed through CO while stirring2、CO2The pressure that is passed through be 0.6Mpa, crystallize
Precipitation obtains methionine crude product；
Above-mentioned methionine crude product is dissolved in sec-butyl alcohol solvent with the concentration of 10mg/mL-20mg/mL, is stirred continuously, adds
Heat, to 60 DEG C～65 DEG C dissolvings, filters, and forms supersaturated solution；This solution is sealed and is placed on crystallisation by cooling 3 in-10 DEG C of environment
Hour, obtain white crystal.
Identify by the method for embodiment 2, for methionine crystal formation I of the present invention, its in water dissolubility at 5.2g/100g water.
Embodiment 4
The preparation method of methionine crystal formation I, employing following steps:
5-(β-first mercaptoethyl) hydantoin react with solution of potassium carbonate obtain containing in methionine potassium hydrolyzed solution
Add the hydroxypropyl methyl cellulose of 900-1000ppm, be passed through CO while stirring2、CO2The pressure that is passed through be 0.2Mpa, tie
Partial crystallization goes out to obtain methionine crude product；
Above-mentioned methionine crude product is dissolved in sec-butyl alcohol solvent with the concentration of 40mg/mL-50mg/mL, is stirred continuously, adds
Heat, to 95 DEG C～100 DEG C dissolvings, filters, and forms supersaturated solution；This solution is sealed and is placed on crystallisation by cooling 1 in-5 DEG C of environment
Hour, obtain white crystal.
Identify by the method for embodiment 2, for methionine crystal formation I of the present invention, its in water dissolubility at 4.6g/100g water.
Embodiment 5
The preparation method of methionine crystal formation I, employing following steps:
5-(β-first mercaptoethyl) hydantoin react with solution of potassium carbonate obtain containing in methionine potassium hydrolyzed solution
Add the hydroxypropyl methyl cellulose of 500-600ppm, be passed through CO while stirring2、CO2The pressure that is passed through be 0.4Mpa, tie
Partial crystallization goes out to obtain methionine crude product；
Above-mentioned methionine crude product is dissolved in sec-butyl alcohol solvent with the concentration of 25mg/mL-35mg/mL, is stirred continuously, adds
Heat, to 70 DEG C～80 DEG C dissolvings, filters, and forms supersaturated solution；The sealing of this solution is placed in-7 DEG C～-8 DEG C of environment and cools down
Crystallize 2 hours, obtain white crystal.
Identify by the method for embodiment 2, for methionine crystal formation I of the present invention, its in water dissolubility at 4.8g/100g water.
Claims (7)
1. a methionine crystal formation I, it is characterised in that: described crystal formation I angle of diffraction 2 θ 21.751 ± 0.2 °, 22.168 ±
0.2 °, 21.186 ± 0.2 °, 25.426 ± 0.2 °, 18.395 ± 0.2 °, have diffraction maximum at 32.879 ± 0.2 °.
2. as claimed in claim 1 methionine crystal formation I, it is characterised in that: described crystal formation at angle of diffraction 2 θ 18.395 ±
0.2°、21.186±0.2°、21.751±0.2°、22.168±0.2°、23.301±0.2°、25.426±0.2°、32.879
± 0.2 °, 33.775 ± 0.2 °, 37.054 ± 0.2 °, have diffraction maximum at 42.455 ± 0.2 °.
3. methionine crystal formation I as claimed in claim 1 or 2, it is characterised in that: the X-ray powder that it has as shown in Figure 1 spreads out
Penetrate figure.
4. methionine crystal formation I as claimed in claim 1, it is characterised in that: it has followingValue and relative intensity hundred
The expression of proportion by subtraction I (%) value-X-ray powder diffraction data,
5. the methionine crystal formation I as described in claim 1,2,3 or 4, it is characterised in that: it has followingValue is with relative
The expression of intensity percent I (%) value-X-ray powder diffraction data:
6. methionine crystal formation I as claimed in claim 1 or 2, it is characterised in that: it has DSC/TG collection of illustrative plates as shown in Figure 2, its
Melting point peak temperature is 282 DEG C.
7. the preparation method of methionine crystal formation I as described in any one of claim 1-6, it is characterised in that employing following steps:
(1), 5-(β-first mercaptoethyl) hydantoin react with solution of potassium carbonate obtain containing in methionine potassium hydrolyzed solution
Add the hydroxypropyl methyl cellulose of 50-1000ppm, be passed through CO while stirring2、CO2The pressure that is passed through be that 0.2-0.6Mpa is left
The right side, carries out crystallization and obtains methionine crude product；
(2), above-mentioned methionine crude product is dissolved in sec-butyl alcohol solvent with the concentration of 10mg/mL-50mg/mL, is stirred continuously, adds
Heat, to 60 DEG C～100 DEG C dissolvings, filters, and forms supersaturated solution；The sealing of this solution is placed in-5 DEG C～-10 DEG C of environment cold
But crystallization 1-3 hour, obtains white crystal.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610391281.7A CN106083675B (en) | 2016-06-03 | 2016-06-03 | A kind of methionine novel crystal forms I and preparation method thereof |
| PCT/CN2017/084383 WO2017206703A1 (en) | 2016-06-03 | 2017-05-15 | Methionine new crystal form i and preparation method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610391281.7A CN106083675B (en) | 2016-06-03 | 2016-06-03 | A kind of methionine novel crystal forms I and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106083675A true CN106083675A (en) | 2016-11-09 |
| CN106083675B CN106083675B (en) | 2018-07-27 |
Family
ID=57447832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610391281.7A Active CN106083675B (en) | 2016-06-03 | 2016-06-03 | A kind of methionine novel crystal forms I and preparation method thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN106083675B (en) |
| WO (1) | WO2017206703A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017206703A1 (en) * | 2016-06-03 | 2017-12-07 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine new crystal form i and preparation method therefor |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4324890B1 (en) * | 1966-08-25 | 1968-10-28 | ||
| CN1274717A (en) * | 1999-05-21 | 2000-11-29 | 住友化学工业株式会社 | Prepn. of methionine |
| CN1589259A (en) * | 2001-11-29 | 2005-03-02 | 日本曹达株式会社 | Process for production of methionine |
| CN1274717C (en) * | 2002-11-06 | 2006-09-13 | 中国人民解放军军事医学科学院附属医院 | Immune suppression fusion protein, its coded nucleic acid and application |
| CN1923807A (en) * | 2005-08-29 | 2007-03-07 | 住友化学株式会社 | Process for producing methionine |
| CN101003822A (en) * | 2006-07-05 | 2007-07-25 | 中国科学院成都有机化学有限公司 | Method for producing D amino acid by immobilizing acylation enzyme of penicillin |
| CN103641758A (en) * | 2013-11-19 | 2014-03-19 | 重庆紫光化工股份有限公司 | Cheap preparation method for high purity D,L-methionine |
| CN104203912A (en) * | 2012-03-20 | 2014-12-10 | 赢创工业集团股份有限公司 | Preparation method of methionine |
| CN104744326A (en) * | 2015-02-12 | 2015-07-01 | 山东新和成氨基酸有限公司 | Method for continuously preparing high-bulk density methionine crystals |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106083675B (en) * | 2016-06-03 | 2018-07-27 | 宁夏紫光天化蛋氨酸有限责任公司 | A kind of methionine novel crystal forms I and preparation method thereof |
-
2016
- 2016-06-03 CN CN201610391281.7A patent/CN106083675B/en active Active
-
2017
- 2017-05-15 WO PCT/CN2017/084383 patent/WO2017206703A1/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4324890B1 (en) * | 1966-08-25 | 1968-10-28 | ||
| CN1274717A (en) * | 1999-05-21 | 2000-11-29 | 住友化学工业株式会社 | Prepn. of methionine |
| CN1589259A (en) * | 2001-11-29 | 2005-03-02 | 日本曹达株式会社 | Process for production of methionine |
| CN1274717C (en) * | 2002-11-06 | 2006-09-13 | 中国人民解放军军事医学科学院附属医院 | Immune suppression fusion protein, its coded nucleic acid and application |
| CN1923807A (en) * | 2005-08-29 | 2007-03-07 | 住友化学株式会社 | Process for producing methionine |
| CN101003822A (en) * | 2006-07-05 | 2007-07-25 | 中国科学院成都有机化学有限公司 | Method for producing D amino acid by immobilizing acylation enzyme of penicillin |
| CN104203912A (en) * | 2012-03-20 | 2014-12-10 | 赢创工业集团股份有限公司 | Preparation method of methionine |
| CN103641758A (en) * | 2013-11-19 | 2014-03-19 | 重庆紫光化工股份有限公司 | Cheap preparation method for high purity D,L-methionine |
| CN104744326A (en) * | 2015-02-12 | 2015-07-01 | 山东新和成氨基酸有限公司 | Method for continuously preparing high-bulk density methionine crystals |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2017206703A1 (en) * | 2016-06-03 | 2017-12-07 | 宁夏紫光天化蛋氨酸有限责任公司 | Methionine new crystal form i and preparation method therefor |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2017206703A1 (en) | 2017-12-07 |
| CN106083675B (en) | 2018-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106432018A (en) | Method for environment-friendly clean production of D,L-methionine | |
| CN104743581B (en) | Preparation technique of high-purity potassium chloride | |
| CN106349131A (en) | Separation and purification method of methionine | |
| CN106478600B (en) | A kind of refining methd of Lansoprazole | |
| CN104788472B (en) | One water Cefazolin sodium spheroidal particle and its crystallization preparation method | |
| CN110527854A (en) | Method for preparing particle size controllable ultra-pure ammonium rhenate crystal | |
| CN104926709B (en) | A kind of process for purification of L tryptophans | |
| CN106083675B (en) | A kind of methionine novel crystal forms I and preparation method thereof | |
| CN105153166A (en) | N- [ (3R,4R) -1-benzyl-4-methylpiperidin-3-yl ] -N-methyl-7H-pyrrolo [2,3-d ] pyrimidin-4-amine crystal | |
| KR100981366B1 (en) | Method for preparing nickel sulfate crystal | |
| CN103833543A (en) | Preparation method of sodium acetate | |
| WO2017206704A1 (en) | Methionine new crystal form ii and preparation method therefor | |
| CN109574047B (en) | Method for recovering high-purity efavirenz and lithium chloride from medical lithium-containing waste liquid | |
| CN103694280A (en) | Method for extracting glucosamine hydrochloride from glucosamine hydrochloride-containing mother liquor | |
| CN110885357B (en) | Method for separating and purifying glutamine dipeptide by nanofiltration membrane | |
| CN109467586A (en) | A kind of refining methd of neotame | |
| CN110606863B (en) | Preparation method of N-acetylneuraminic acid dihydrate | |
| CN102702005A (en) | Trans-tranexamic acid purifying method | |
| CN104447432B (en) | A kind of preparation method of new sulfonation dehydrogenation rosin acid bismuth | |
| EP4296263A1 (en) | High-efficiency cyclic preparation method for columnar taurine | |
| CN102358720A (en) | Dilution crystallization method for preparing anhydrous L-phenylalanine | |
| CN107245031A (en) | A kind of preparation method that mould inhibitor is made by anhydrous sodium acetate | |
| CN103864676A (en) | Methods for improving production process of paraquat and obtaining crystals | |
| CN109535028B (en) | Method for preparing pure anilinoacetonitrile by suspension melting crystallization method | |
| CN113512012A (en) | Continuous evaporative crystallization system and method for preparing acesulfame potassium |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A new methionine crystal form I and its preparation method Effective date of registration: 20200904 Granted publication date: 20180727 Pledgee: Chongqing chemical medicine holding (Group) Co.,Ltd. Pledgor: NINGXIA UNISPLENDOUR TIANHUA METHIONINE Co.,Ltd. Registration number: Y2020500000011 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230711 Granted publication date: 20180727 Pledgee: Chongqing chemical medicine holding (Group) Co.,Ltd. Pledgor: NINGXIA UNISPLENDOUR TIANHUA METHIONINE Co.,Ltd. Registration number: Y2020500000011 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A new crystal form I of methionine and its preparation method Effective date of registration: 20230725 Granted publication date: 20180727 Pledgee: Chongqing chemical medicine holding (Group) Co.,Ltd. Pledgor: NINGXIA UNISPLENDOUR TIANHUA METHIONINE Co.,Ltd. Registration number: Y2023500000053 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right |